YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
80 巻, 4 号
選択された号の論文の33件中1~33を表示しています
  • 粉末接触融解法による有機化合物の共融点測定について
    穂積 啓一郎, 森田 舒子
    1960 年 80 巻 4 号 p. 403-406
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The microscopic mixed fusion technique proposed by Kofler is a valuable method in furnishing numerous observations regarding eutectic melting of two-componental system and formation of molecular compounds. However, this technique requires pretreatment of the sample by fusion and recrystallization to prepare the test piece. The technique cannot be applied to substances which undergo decomposition by fusion or which cannot be recrystallized. In such cases, the two components are separately reduced to a fine powder, about 1mg. of each is placed on a slide glass, about 5mm. apart as shown in Fig. 2, and the powder is rubbed gently with a cover glass placed over them, so as to contact the two components partially. Heating of this powder results in appearance of a line of eutectic melt in the center of the contact zone. In this procedure, change of contact zone can be observed in comparison with pure components so that the identification of the eutectic point becomes more accurate. Further, the process can be utilized for the judgement of identity or differentiation of two substances and for examination of purity.
  • 粉末接触融解法によるスルファミン, ビタミンB, アミノ酸類の共融点測定について
    穂積 啓一郎, 森田 舒子
    1960 年 80 巻 4 号 p. 407-409
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Sulfanilamides, vitamin B group compounds, and amino acids have generally high melting point and majority do not show a definite melting point. For such substances, measurement of a eutectic point with a suitable standard reference substances is recommended in place of melting point determination. The use of the powder mixed fusion technique enables measurement of a more reliable eutectic point without introduction of subjective view. Values obtained by such method are listed in Tables I, II, and III. In general, dicyanodiamide forms a good eutectic mixture with these substances and depression of the melting point is also great.
  • 検圧法による微量接触還元・活性水素定量装置について
    穂積 啓一郎
    1960 年 80 巻 4 号 p. 410-414
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    In micro-catalytic hydrogenation, the construction of glass apparatus is more simple in manometric method than the volumetric method. On the other hand, it is necessary to accurately determine the internal volume of an apparatus prior to analytical procedure and this was extremely complicated in the apparatus of the existing type. The new manometric apparatus shown in Fig. 1, can be filled with water easily and internal volume can be measured in a short period of time. The manometer in this apparatus is a simple U-tube so that variation in mercury level would cause variation in internal volume but it was found from calculations that in the apparatus of the size as shown in Fig. 1, 2% correction of the observed value is sufficient. It is possible to carry out quantitative determination of active hydrogen by lithium aluminum hydride with this apparatus merely by changing the content of the reaction vessel.
  • Lg(+)-threo-2,2-Dimethyl-4-phenyl-5-amino-1,3-dioxaneの脱アミノ化
    紙谷 孝, 田中 邦彦
    1960 年 80 巻 4 号 p. 414-417
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Deamination of Lg(+)-threo-2, 2-dimethyl-4-phenyl-5-amino-1, 3-dioxane (I) with nitrous acid afforded β-hydroxypropiophenone (III) in 70% yield, together with about 3% of cinnamaldehyde. From this result, it was revealed that the preferred conformation of (I) is an axial amino group and equatorial phenyl, and the deamination would be the same as that in cyclohexane series. Reduction followed by diacetylation of (III) afforded 1-phenyl-1, 3-diacetoxypropane (VIII), whose pyrolysis and hydrolysis gave cinnamyl alcohol. 1-Phenyl-2-bromo-1, 3-propanediol (XI) was derived from (III).
  • Lg(+)-threo-2,2-Dimethyl-4-phenyl-5-amino-1,3-dioxaneのDg(-)-threo体への転換 その1
    紙谷 孝
    1960 年 80 巻 4 号 p. 417-424
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Oxidation of Lg(+)-threo-(I) with potassium permanganate affords Lg(-)-oxime (II) and Lg(+)-threo-(III). Oxidation with perbenzoic acid of the same compound affords 70-75% of Lg(-)-oxime (II) and 7-10% of Lg(+)-threo-nitroso dimer (VII). Thermal depolymerization of (VII) effects almost quantitative rearrangement to Lg(-)-oxime (II). (II) is resistant to reducing agents in general but its reduction with lithium aluminum hydride or over Raney nickel under high pressure affords a mixture of Lg(+)-threo-(I) and Lg(-)-erythro-(I) in respective yield of 90-95% and 80-85%. The mixture ratio is approximately 1:2 of threo to erythro by reduction with lithium aluminum hydride and approximately 10:1 of threo to erythro by Raney nickel under high pressure, as evidenced by isolation of dichloroacetyl compounds (X). Lg(-)-erythro-(X) was proved by its derivation to Dg(-)-(XII).
  • Lg(+)-threo-2,2-Dimethyl-4-phenyl-5-amino-1,3-dioxaneのDg(-)-threo体への転換 その2
    紙谷 孝
    1960 年 80 巻 4 号 p. 424-429
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The mode of reduction of Lg(+)-oxime (II) was utilized for conversion of Lg(+)-threo-(I) to Dg(-)-threo-(I). Dg(+)-erythro-(V) was prepared by the known method and cyclized by acetone to Dg(+)-erythro-(I), whose oxidation with perbenzoic acid afforded chiefly Dg(-)-erythro-nitroso-dimer (XVII) and a small amount of Dg(+)-oxime (II) as a by-product. Thermal depolymerization of the nitroso-dimer (XVII) afforded Dg(+)-oxime (II) which was reduced under high pressure to Dg(-)-threo-(I). The mechanism of oxidation of threo-(I) and erythro-(I) with perbenzoic acid was assumed to be controlled by the conformation of the nitroso compound (XVI) formed as an intermediate.
  • N-(5-ハロゲンフルフリリデン)-アリルアミンの合成ならびにアミン類との反応
    島村 真一
    1960 年 80 巻 4 号 p. 429-434
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Fourteen kinds of N-(5-halofurfurylidene)-arylamine (B) (Table I) was prepared by the reaction of 5-halofurfural (halogen=Cl or Br) and aromatic primary amines in cold ether solution. (B) was also formed by the reaction of 5-halofurfural and N-benzylidenearylamine. Of the compounds (B) so formed, N-(5-halofurfurylidene)-anilines (I and X) reacted with aniline to produce N-(5-anilinofurfurylidene)-anilines (A), and with sodium ethoxide to form N-(5-ethoxyfurfurylidene)-aniline, (B) formed (A) on merely heating (B) with alcohols and this reaction mechanism was assumed to be as indicated by formulae (3), (4), and (1).
    Application of benzylamines to (I) was found to effect exchange reaction of the amines. Reduction of (X) with sodium borohydride to N-(5-bromofurfuryl) aniline and its reaction with aniline ended in complete recovery of the starting compound.
  • N-(5-ハロゲンフルフリリデン)-アリルアミンに対する別種の芳香族第一級アミンの反応
    島村 真一
    1960 年 80 巻 4 号 p. 435-438
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reaction of N-(5-halofurfurylidene)-arylamine with different kind of primary amines was found to result in establishment of the relationship indicated by formula (5). For example, reaction of N-(5-bromofurfurylidene)-aniline and m-toluidine gives, not N-(5-m-toluidinofurfurylidene)-aniline hydrobromide but N-(5-anilinofurfurylidene)-m-toluidine hydrobromide. The same compound is obtained even on reacting 1 mole each of 5-bromofurfural, aniline, and m-toluidine.
  • tert-ブチルヒドロペルオキシドによる亜リン酸トリエステルの酸化
    田中 照夫
    1960 年 80 巻 4 号 p. 439-442
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Phosphorus triesters are readily oxidized in tert-butanol to corresponding phosphoric triesters by tert-butyl hydroperoxide. By this method, triphenyl, diphenyl butyl, dibutyl phenyl, tributyl, and tris (2-chloroethyl) phosphates were obtained in 50-90% yield. Using this reaction, O-phosphorylethanolamine and dl-glycerol 1-phosphate were obtained from N-benzyloxycarbonylethanolamine and dl-isopropylideneglycerol, respectively, by (1) the reaction of alcohols with diphenyl phosphorochloridite, (2) oxidation of the resulting diphenyl alkyl phosphite to phosphate with tert-butyl hydroperoxide, and (3) removal of protective groups.
  • Tschugaeff反応機構の検討 その1 コレステロールと塩化亜鉛の反応成績体について
    渡辺 俊雄
    1960 年 80 巻 4 号 p. 442-445
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine the Tschugaeff reaction, each of the coloration reagents for cholesterol, acetyl and zinc chlorides were examined. In the case of acetyl chloride, substances other than acetylated product were not obtained, while dehydrated and polymerized products were obtained in the case of zinc chloride. Heating of cholesterol and zinc chloride in solid state, in nitrogen stream, results in formation of cholestadiene and bicholestadienyl, and the latter is also obtained on heating in acetic acid or acetic anhydride. In acetic acid solution, acetylation occurs at room temperature when zinc chloride is present. When the solution of cholesterol in acetic acid-benzene mixture is added with zinc chloride, three kinds of molecular addition compounds with different ratios are obtained, and those in which the molar ratio of cholesterol to zinc chloride is 1.5 and 2 moles are colored (reddish).
  • Tschugaeff反応機構の検討 その2 呈色物質およびその反応機構について
    渡辺 俊雄
    1960 年 80 巻 4 号 p. 445-451
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    When the Tschugaeff reaction is carried out in methylene chloride, the color developed becomes brighter. Of the colored substances formed, the red colored substance formed with cholesterol tends to be discolored by sunlight. This substance contains zinc and purification with removal of zinc gives cholesteryl acetate. In the Tschugaeff reaction, red substance (R) is formed from the reagents alone, acetyl chloride and zinc chloride. Warming the chloroform solution of various steroids with this red substance results in the formation of a substance whose absorption spectra in the range of 320-600mμ are the same as that in the case of coloration by the Tschugaeff reaction. For example, the product obtained by reaction with ergosterol colors green and its absorption maximum is the same as that of the product from the Tschugaeff reaction. Warming of the chloroform solution of cholesterol or ergosterol and the red substance (R) results in dehydration and rearrangement of the double bond, giving a hydrocarbon containing zinc from cholesterol. It was assumed that when the B-ring in unsaturated steroid is active, it undergoes addition with (R) and forms one of the colored products from the Tschugaeff reaction. Cortisone acetate, which does not give any marked coloration by the Tschugaeff reaction, afforded two kinds of crystalline substances in which the double bond had undergone rearrangement. The reaction product from cholesterol afforded 3, 5-cholestadiene and 3, 3′-bis-2, 4-cholestadienyl.
  • dl-2,2´-Bis (2-methyl-6,7-dimethoxy-1,2,3,4-tetrahydro-1-isoquinolylmethyl) diphenyl Etherの合成
    新美 仁作
    1960 年 80 巻 4 号 p. 451-456
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    A biscoclaurine-type base was prepared by the Ullmann reaction of two kinds of benzyltetrahydroisoquinoline-type bases. One of the starting compounds, dl-1-(2-hydroxybenzyl)-2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (XIV) was prepared by the route shown in Chart 1 and its Ullmann condensation with dl-1-(2-bromobenzyl)-2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (XV) afforded dl-2, 2′-bis (2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydro-1-isoquinolylmethyl) diphenyl ether (XVI).
  • 有機フッ素分析に関する研究
    小野江 敏浩
    1960 年 80 巻 4 号 p. 456-460
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made on the determination of organic fluorine compounds in which the fluorine compound is burned in a quartz combustion tube in oxygen stream and the fluoride formed is absorbed by a reagent filled in a quartz absorption funnel with cap. Experiments were made with NaF, MgO, ZrO2, CeO2, MnO2, PbO2, and Fe2O3 as the fluoride-absorbing agent and Fe2O3 showed the best absorptivity. When an organic fluorine compound is burnt, fluorine changes into hydrogen fluoride and reacts with quartz to form silicon tetrafluoride, but a part of it is still in equilibrium with hydrogen fluoride and reacts as shown by equation (1). In the present series of experiments, the determination was carried out with an apparatus shown in Fig. 1, the sample was burnt, the fluoride formed was absorbed by an absorption funnel filled with granular Fe2O3, and the amount of fluorine was calculated from the increase in weight of the funnel. Analytical values so obtained tended, to be smaller and this was attributed to the trace of boron contained in the combustion tube which had reacted with fluorine to form boron trifluoride.
  • 血漿中アンチピリンの比色定量
    南原 利夫
    1960 年 80 巻 4 号 p. 460-464
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new colorimetric method for antipyrine was studied and the standard procedure was established. Its principle, described by Feigl, et al., is based upon the fact that antipyrine readily yields 4-nitroso derivative with nitrous acid, which condenses with primary amines in acetic acid solution to form an azo dye. It has been found that 4-amino-5-hydroxynaphthalene-1-sulfonic acid (S-acid) colors blue violet (λmax 565mμ) under the above condition and is a suitable reagent for the colorimetric determination of antipyrine. Using the calibration curve by the standard procedure, a known amount of antipyrine added to plasma was measured and its recovery was only 91.2±1.5%. It is therefore necessary to correct it for the estimation of antipyrine in plasma by this method.
  • 鳩法による各種新強心配糖体の致死量測定
    岡野 淳二, 笠原 明, 大島 康夫
    1960 年 80 巻 4 号 p. 465-468
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Lethal doses (pigeon) were measured of the new cardiotonic glycosides reported to date in papers of this series, i.e. gitostin, neogitostin, and glucodigifucoside, the known glycosides, i.e. digitalinum verum, digitoxin, strospeside, and purpurea glycoside-B, and acetyl derivatives such as 16-acetyl-digitalinum verum derived chemically from digitalinum verum, and relationship between their chemical structure and toxicity was comparatively examined. An interesting fact was thereby found that 16-acetyl-digitalinum verum was about five times stronger than digitalinum verum.
  • Azophenol系化合物の真菌に対する抗黴作用についての検索
    山添 寛
    1960 年 80 巻 4 号 p. 468-474
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    In vitro growth-inhibitory effect was examined with 56 kinds of azophenol series compounds, having 4-phenylazophenol as the fundamental skeleton and halogen or various other substituents introduced into its benzene ring, and three kinds of other azo compounds, using trichomycin, 10-hydroxy-11-hydroxymercuriundecanoic acid, and phenol as the controls, with Trichophyton asteroides, T. interdigitale, T. schoen-leinii, Microsporum gypseum, Epidermophyton floccosum, and Candida albicans as the test fungi. It was found that 4-(4-nitrophenylazo)-2-chlorophenol was able to inhibit the growth of test fungi in high dilutions of 1:1, 280, 000 to 1:2, 560, 000.
  • 森川 利秋
    1960 年 80 巻 4 号 p. 475-480
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Amino- and dimethylamino-α, ω-diphenylalkanes possessing normal alkyl chain of 1-5 carbon atoms and an amino or dimethylamino group on either end of the chain, and their methiodides were prepared, and resolution of the compounds possessing asymmetric carbon atom into optical antipodes was attempted as tartrates. The compounds possessing a substituent in the carbon adjacent to the phenyl group were successfully resolved but those with the substituent bonded to the same carbon as that carrying the phenyl group could not be resolved.
    Antihistamine and anticholinergic activity of these compounds was examined by the Magnus method. Pharmacological action of these compounds became stronger with increasing number of carbon atoms in the 3-alkyl group, becoming maximum at alkyls of 3-5 carbon atoms, and becoming weaker thereafter. Among the methiodides, the compound with alkyl group with 1 carbon atom showed cholinergic activity, the action became anticholinergic in that with 2 carbon atoms, and the anticholinergic action became stronger with the increase of carbons from 3 to 5. This is in good agreement with observations made in the case of N, N, N-trimethyl salts. In compounds having the same number of carbon atoms, the pharmacological activity became stronger as the position of substituent became closer to the phenyl group. The foregoing experimental results are in good agreement with those obtained by Ogata and on local anesthetic acitivity of amino compounds.
  • 森川 利秋
    1960 年 80 巻 4 号 p. 481-486
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Fourteen kinds dimethylamino-1, 1-diphenylalkane, with straight-chain alkyls of 1-5 carbon atoms, and their methiodides were prepared. The intensity of antihistamic and anticholinergic activity of these compounds, tested by the Magnus method, became stronger as the position of the functional group moved away from the phenyl group, became the maximum at alkyls with 3-5 carbon atoms, and decreased thereafter. The presence of alkyl group in carbon atoms away from that bonded with functional group generally lowers the activity, but fortifies the anticholinergic activity in methiodides. Pharmacological activity of amines, dimethylamines, and their methiodides possessing alkyl, phenylalkyl, 2-pyridylalkyl, alkyls with phenyl group on either end, and alkyls with two phenyl groups on one end, is dependent on the overall size and length of the portion bonded with functional group in intensity and activity. When the diameter of a benzene ring is taken as the length of a carbon chain with approximately 3.2 carbon atoms and the value is added to that of the alkyl group, the intestinal contraction action in the methiodides gradually increases with increasing number of carbon atoms in the alkyl chain up to 4-5 and decreases with increasing number (up to 7-8) of carbon atoms thereafter. In compounds possessing a benzene ring, the action changes to intestinal alleviation from this point, which action gradually becomes stronger, reaching the maximum at 9.4-11.4 carbon atoms, and becomes weaker thereafter. The peak of intestinal alleviation action in the amino and dimethylamino compounds possessing two phenyl groups is also present at the same number of carbon atoms.
  • フェノール類の呈色反応機構 その2 ペンタシアノ鉄錯塩とヒドロキシルアミンの反応ならびにフェノール類の呈色溶液の吸収スペクトルについて
    大熊 誠一
    1960 年 80 巻 4 号 p. 487-493
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Sodium nitroprusside, pentacyanoaquoferroate, and pentacyanoammineferroate react with hydroxylamine in caustic alkali solution and form the same iron (II) complex salts with absorption maximum at 386-389mμ. It was revealed through absorption spectra, paper chromatography, and paper electrophoresis that these three compounds react with phenols in the presence of hydroxylamine to form the same anionoid dye. Phenols with electron-releasing group forms a colored solution with absorption maximum at 690-710mμ, and those with electron-attracting group forms a solution with absorption maximum at 710-740mμ. In this reaction, phenols with a substituent in para-position, with the exception of p-aminophenol, generally showed weak reaction or did not react at all.
  • フェノール類の呈色反応機構 その3 p-Aminophenol類を配位子としたペンタシアノ鉄錯塩およびインドフェノール型色素生成について
    大熊 誠一
    1960 年 80 巻 4 号 p. 493-498
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Mechanism of color reaction of phenols by the reaction of pentacyano-iron complex like sodium nitroprusside and pentacyanoammineferroate, and hydroxylamine was examined by paper chromatography, paper electrophoresis, and absorption spectra. It was revealed that the chief product of this reaction is blue or green pentacyano-p-aminophenolf erroates. In the case of phenols with electron-releasing group, a part of the p-aminophenols formed by the reaction and unchanged phenols undergo autoxidative condensation to produce the indophenol-type dye as a by-product.
  • フェノール類の呈色反応機構 その4 Pentacyano-p-aminophenolferroateの単離ならびにその生成機構について
    大熊 誠一
    1960 年 80 巻 4 号 p. 499-504
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The colored substance formed by coloration reaction of phenol between pentacyano-iron complex salts and hydroxylamine was isolated as the bluish violet solid Zn3 [Fe(CN)5NH2C6H4OH]2⋅6H2O, by liquid chromatography through alumina, preliminarily washed with 2N acetic acid and water, and developed with 0.05N sodium hydroxide solution. The organic ligand in the colored iron complex salt was identified as p-aminophenol by elemental analysis, infrared absorption spectrum, and isolation of p-aminophenol dibenzoate by the sodium hyposulfite-benzoyl chloride-sodium hydroxide method. The amination reaction of phenols by pentacyano-iron complex and hydroxylamine occurs by initial introduction of hydroxylamine as a ligand into the complex group in pentacyanoaquoferroate or pentacyanoammineferroate to form pentacyanohydroxyaminoferroate and attacks the para-position of the phenolic hydroxyl. This was used for explanation of the mechanism of coloration reaction.
  • ニトロプルシッドナトリウムとフェリシアン化カリウムによるグアニジン塩基の呈色反応 その1 ニトロプルシッドナトリウムとフェリシアン化カリウムの反応について
    大熊 誠一
    1960 年 80 巻 4 号 p. 505-511
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reaction of sodium nitroprusside and potassium ferricyanide was followed by absorption spectrum and paper electrophoresis, using 0.5% KCl as the electrolyte solution, at 10V/cm., for 60 minutes. The nitroprusside and potassium ferricyanide react in caustic alkali solution to form pentacyanoaquoferroate and ferrocyanide (II). The chemical reaction of sodium nitroprusside in this reaction may be represented as sequential change from the nitroprusside through pentacyanonitrito-ferroate and pentacyanoaquoferroate, to pentacyanoaquoferriate (III) (Chart 1). Potassium ferricyanide effects oxidation of the pentacyanoaquoferroate to (III) while (II) itself is reduced and accelerate the reaction of the nitroprusside to the aquo complex.
  • ニトロプルシッドナトリウムとフェリシアン化カリウムによるグアニジン塩基の呈色反応 その2 ペンタシアノアクオフェロエートとグアニジン塩基の反応について
    大熊 誠一
    1960 年 80 巻 4 号 p. 511-515
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Coloration reaction of guanidine bases by sodium nitroprusside and potassium ferricyanide was examined through absorption spectrum. This coloration reaction is a formation of colored pentacyano-iron complex salts between guanidine bases and pentacyanoaquoferroate formed by hydration of sodium nitroprusside. It was revealed that in this reaction, potassium ferricyanide accelerates both the hydration of sodium nitroprusside and formation of the colored pentacyano-iron complex salts at the same time. A mixed reagent of sodium pentacyanoammineferroate and potassium ferricyanide is a far better colorimetric reagent for guanidine bases than the mixed reagent of sodium nitroprusside and potassium ferricyanide with respect to the stability and intensity of the coloration.
  • スルファミン類の定量
    棚瀬 彌一郎, 下村 滋
    1960 年 80 巻 4 号 p. 516-519
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Since the nitrite ion has absorption maximum at 355mμ, photometric titration was carried out with the spectrophotometer set at 355mμ. It was found that sulfanilamide and sulfacetamide could be determined with good accuracy without being affected by the absorption of their own diazonium salts at 355mμ. In the case of sulfaguanidine, sulfathiazole, sulfadiazine, and sulfamerazine, the absorption of the respective diazonium salts formed affects absorption at 355mμ. Absorption spectra of these sulfonamides were therefore measured over the whole range of ultraviolet region before, during, equivalence point, and excess of titration. The spectrophotometer was then set at the determined wave length and determination was carried out, by which it was found that the determination of these sulfonamides was possible, as in the case of sulfanilamide and sulfacetamide. This kind of photometric titration has smaller individual difference than the existing method using zinc iodide-starch solution as an indicator. Consequently, determination of sulfanilamides by photometric titration makes it possible to calculate the amount of sulfanilamides from the crossing of two straight lines and the determination can be made with a minute amount of sample.
  • ヨウ素, 臭素イオンおよび塩素イオン存在下におけるヨウ素イオンの定量について
    棚瀬 彌一郎, 下村 滋
    1960 年 80 巻 4 号 p. 520-524
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Potassium iodide was titrated in 2-15% sulfuric acid solution with 0.02N or 0.001N potassium permanganate and this titration was followed by absorption at 290mμ, the absorption maximum of the periodide ion, and photometric titration curve shown in Fig. 2 was obtained. This curve was understood to mean that, when periodide ion, with absorption maximum at 290mμ, is formed when I2 separates out from I-, the absorbance increases until equilibrium is reached, the absorbance decreases thereafter as I2 forms in excess, and the minimum absorbance is shown when all I- turns into I2. At this point, 1cc. of 0.001M KI was calculated to correspond to 1cc. of 0.001N KMnO4 and the value agreed entirely with the theoretical value. This method is not affected by the presence of Cl-, Br-, and I2, so that it is considered to be suitable for determination of a trace (0.001-0.0001M) of I- in the presence of those halogens. However, the process is affected by the presence of alcohol and the method cannot be used for determination of preparations containing alcohol.
  • 3-Acylamino-4-hydroxycoumarin誘導体の合成
    奥村 健太郎
    1960 年 80 巻 4 号 p. 525-532
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine the antibacterial and antifungal activities of novobiocic acid derivatives, preparation of 3-acylamino-4-hydroxy- and 3-acylamino-4, 7-dihydroxy-coumarins, and their 7-acyloxy derivatives was carried out. Coupling of 4, 7-dihydroxycoumarin with benzenediazonium chloride gave 7-hydroxy-2, 3, 4-trioxochromone 3-phenylhydrazone whose catalytic reduction over palladium-carbon afforded 3-amino-2, 7-dihydroxychromone hydrochloride in a good yield. Reaction of acid chloride with 3-amino-4-hydroxycoumarin and 3-amino-2, 7-dihydroxychromone hydrochloride in pyridine gave various 3-acylamino and 3-acylamino-7-acyloxy derivatives. It was revealed that 3-acylamino-dihydroxy derivatives took one or the other of 4, 7-dihydroxycoumarin and 2, 7-dihydroxychromone structures according to the kind of acyl group substituted. Examination of antibacterial and antifungal activities of these novobiocic acid derivatives synthesized showed that some of them are effective.
  • 酸化還元系滴定における交流分極電流滴定
    森坂 勝昭, 原田 多賀子
    1960 年 80 巻 4 号 p. 532-537
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Amperometric polarization titration by A. C. requires consideration of the resistance of the solution to be titrated (titrant), or the electric conductivity and polarization resistance of the electrode or double polarization phenomenon. In order to effect titration, it is necessary to have polarization resistance as sharp as possible. It was found possible to obtain titration with sufficient sensitivity by the use of an electrode with supermicro surface area and by using A. C. in which wave cycle is comparatively low. It was found that the addition of a large amount of electrolytes indifferent to titration increased the sensitivity and that there is no effect of the rate of stirring of the solution, which facts are different from those seen in the use of D. C. Some theoretical and experimental results are described.
  • 白金電極を用いての交流分極電流法における硝酸銀滴定について
    森坂 勝昭, 原田 多賀子
    1960 年 80 巻 4 号 p. 537-541
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    As an application of A. C. polarographic titration with platinum electrode, titration with silver nitrate was attempted. Titration conditions for A. C. polarographic titration require extremely small electrode surface area, large concentration of unrelated electrolyte, and low A. C. cycles. It is considered that the platinum electrode has different surface conditions in A. C. and D. C., and it was found that the silver ion acts as a reaction agent at the electrode, even without addition of an additive like hydrogen peroxide, making it possible to carry out polarographic titration. When the titration conditions are in reverse of those for polarographic titration, the present method of titration tends to be a conductometric titration. It follows, therefore, that the titration curve thought to be intermediate of these two titration methods will be obtained according to the selection of titration conditions. In any case, the present method of titration makes it possible to carry out silver nitrate titration easily. Comparison was made on titration curves to examine titration conditions and considerations were made on the present method of titration.
  • 白金電極を用いての交流分極電流法における中和滴定について
    森坂 勝昭, 原田 多賀子
    1960 年 80 巻 4 号 p. 541-544
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Neutralization method was attempted as an application of A. C. polarographic titration by platinum electrodes and results similar to those from silver nitrate method were obtained. In other words, polarographic titration is possible without any additive as long as the surface area of the electrode is extremely small, nonrelative electrolyte concentration is large, and A. C. cycles are low. It is considered that H+ and OH- react on the platinum electrode in this case and OH- shows especially marked electrode reactivity. When the titration conditions are reverse of those in polarographic titration, the method has a tendency to behave like conductometric titration. Therefore, this titration method also shows behavior intermediate of polarographic and conductometric titrations. In any case, the results obtained were those of electrometric titration method, different from those using D. C.
  • テトラサイクリンの比色定量法
    村井 好之助
    1960 年 80 巻 4 号 p. 544-547
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Numerous reports have been published regarding colorimetric determination of tetracycline but the present series of experiments were carried out in order to find a simple and more practicable method for chemical determination. The sample solution is prepared by dissolving tetracycline hydrochloride in distilled water to make a solution containing 10-100γ of tetracycline hydrochloride in 1cc. of the solution. A. 1cc. portion of this solution is placed in a glass-stoppered test tube, 2cc. of Mcllvain buffer (pH 7.0) and 0.2cc. of 0.05% aqueous solution of dimethyl-p-phenylenediamine hydrochloride are added, and mixed thoroughly. This solution, after addition of 3cc. of isobutanol and 0.2cc. of 0.02% aqueous solution of sodium hypochlorite, is shaken vigorously for 3 minutes and allowed to stand for 5 minutes at room temperature (5-30°). The blue-colored isobutanol layer is transferred to a dry test tube, 0.2cc. of absolute ethanol is added, and absorbance of this solution is measured at 630mμ. This method allows determination of a microquantity by a comparatively simple procedure and is also possible to determine the quantity of tetracycline in its preparation containing sodium metaphosphate and in tetracycline metaphosphate preparation, and also separatory determination of tetracycline in a mixture of tetracycline and chlorotetracycline.
  • 新葉および老葉に対する15Nの吸収
    井上 隆夫, 山下 三郎, 川村 八重子, 佐々木 〓郎
    1960 年 80 巻 4 号 p. 548-551
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Biogenesis of caffeine in tea leaves was followed by tracer technique, and in order to examine the effect of nitrogenous fertilizer on cultivation, tea trees were cultivated for about three months during autumn to winter using a medium containing (15NH4)2⋅SO4 (Expt. I). It was thereby learned that about one-half of the 15N absorbed was stored in the root while the other half transited to the aerial portion. In the young leaves, 40% of 15N and 70% of it in old leaves were found in the protein. Fresh caffeine produced from the absorbed labeled nitrogen was only 0.46% (Tables III and V).
    After three months of cultivation, a part of the tea trees was transplanted to 15N-free soil and further cultivated for about four months, until the following spring (Expt. II). It was found that 15N of proteins in the root decreased while concentration of 15N in the leaves showed general increase. This fact seemed to suggest that 15N stored in the root during autumn to winter had been utilized next spring for formation of caffeine. It was found also that incorporation of 15N into caffeine occurs much later than that into the proteins.
  • 小川 信久, 小宮 清一郎, 小川 昭子, 持田 英
    1960 年 80 巻 4 号 p. 552-554
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    No report has been made on the protease contained in testicular tissue but its presence was detected in the crude hyaluronidase prepared by ammonium sulfate fractionation. This protease had optimal pH in the weakly acid range and was most stable at around pH 6. When left at pH 9 and 37°, in the presence of sodium chloride, the majority of protease activity could selectively be inactivated practically without any harm on the hyaluronidase activity.
  • 藪内 隆弘
    1960 年 80 巻 4 号 p. 554-557
    発行日: 1960/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Attempt was made on the acylation of free organic acid with phenol and aromatic amines by removing the water formed by the reaction through azeotropic distillation. Boric acid and p-toluenesulfonic acid were used as the catalytic agent in this reaction. By this reaction, phenyl acetate, phenyl propionate, phenyl benzoate, p-tolyl acetate, p-tolyl propionate, o-methoxyphenyl acetate, acetanilide, p-chloroacetanilide, and p-acetotoluidide were prepared. Acylation of free acid with phenol was effected by the addition of boron trioxide. Acylated products of alcohols and aromatic amines were obtained in a good yield by this method. Acylation of phenols with free acid is generally difficult and the present process is an interesting one in organic chemical reaction.
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